Photoanode of LDH catalyst decorated semiconductor heterojunction of BiVO4/CdS to enhance PEC water splitting efficiency

BiVO₄ is an ideal photoanode material for solar-driven photoelectrochemical (PEC) water splitting but it easily suffers from the recombination of photogenerated electrons and holes due to its low carrier mobility thus cause low efficiency of PEC water splitting. Herein, the BiVO₄/CdS/NiCo-LDH photoanode was prepared by combining methods of metal organic decomposition, chemical and electrodeposition. The photoanode photocurrent density reaches 2.72 mA cm⁻² at 1.23 V (vs. RHE), which is 3.6 folds of pure BiVO₄ photoanode and onset potential shifts 450 mV toward cathodic. The incident photon-to-electron conversion efficiency (IPCE) value is 2.86 folds of BiVO₄, the calculated photon–to–current efficiency (ABPE) is 1.24% at 0.62 V (vs. RHE). The obtained results are higher than that of most BiVO₄ based photoanodes published so far. The enhancement benefits from increase of visible light absorption capacity, enhancement of separation efficiency of photoexcited electron-hole and fast transfer of holes accumulated on electrode/electrolyte surface for water oxidation, which has been confirmed by calculating carrier density and carrier transport rate.     

Polythiophene coated CuBi2O4 networks: A porous inorganic–organic hybrid heterostructure for enhanced photoelectrochemical hydrogen evolution

A thin porous film inorganic-organic heterostructure photocathode has been successfully fabricated and applied in photoelectrochemical (PEC) water splitting. Our work optimized the best structure of CuBi₂O₄ (CBO) base on FTO (fluorine doped tin oxide). Furthermore, it was passivated with polythiophene (PTh), a kind of conducting polymers of excellent environmental and thermal stability, to decrease the capture ability of surface state for photogenerated charge. Benefiting from the high light capture rate of porous structure of CBO and low electron-hole recombination rate of CBO/PTh heterojunctions, the as-fabricated FTO/CBO/PTh electrode delivers excellent PEC performance with a ultimate photocurrent density of 0.41 mA cm^?2 at 0.3 V vs RHE (reversible hydrogen electrode) doubled to that of pure FTO/CBO electrode, which would be due to the significantly improved light absorption and rapid separation efficiency.     

Chemical bath deposition synthesis of TiO2/Cu2O core/shell nanowire arrays with enhanced photoelectrochemical water splitting for H2 evolution and photostability

In this study, we have developed a facile chemical bath deposition (CBD) method to grow p-type Cu₂O nanoparticles on n-type TiO₂ nanowire arrays (TiO₂ NWAs) to fabricate TiO₂/Cu₂O core/shell heterojunction nanowire arrays (TiO₂/Cu₂O core/shell NWAs). When used as photoelectrode, the fabricated TiO₂/Cu₂O core/shell NWAs show improved photoelectrochemical (PEC) water splitting activity to pure TiO₂ NWAs. The effects of the CBD cycle times on the PEC activities have been studied. The TiO₂/Cu₂O core/shell heterojunction nanowire array photoelectrode prepared by cycling 5 times in the CBD process achieves the highest photocurrent of 2.5 mA cm^?2, which is 2.5 times higher than that of pure TiO₂ NWAs. In addition, the H₂ generation rate of this photoelectrode reaches to 32 μmol h^?1 cm^?2, 1.7 times higher than that of pure TiO₂ NWAs. Furthermore, the TiO₂/Cu₂O core/shell heterojunction nanowire array photoelectrode shows excellent photostability and achieves a stable photocurrent of over 2.3 mA cm^?2 during long light illumination time of 5 h. The enhanced photocatalytic activity of TiO₂/Cu₂O core/shell heterojunction nanowire array photoelectrode is attributed to the synergistic actions of TiO₂ and Cu₂O for improving visible light harvesting, and efficient transfer and separation of photogenerated electrons and holes.     

Enhancement of photoelectrochemical activity of Fe2O3 nanowires decorated with carbon quantum dots

Owing to its up-conversion photoluminescence, photo-induced electron transfer property, and excellent conductivity, carbon quantum dots (CQDs) have been established as effective sensitizers in combination with Fe₂O₃ nanowires for enhancing the catalytic activity of photoelectrochemical water oxidation. In comparison to pristine Fe₂O₃ nanowires, Fe₂O₃ nanowires decorated with CQDs demonstrate 27 orders of magnitude increase in photocurrent density at 0.23 V vs. Ag/AgCl. The mechanism of enhanced photoelectrochemical activity of CQDs/Fe₂O₃ composite was also investigated. Thereby, it is confirmed that the enhanced optical absorption, accelerated interfacial charge carrier transfer and effective separation of photogenerated electron-hole pairs induced by CQDs decoration account for the enhancement of CQDs/Fe₂O₃ nanowire arrays in photoelectrochemical application.     

Simultaneously efficient light absorption and charge transport of CdS/TiO2 nanotube array toward improved photoelectrochemical performance

CdS has been widely used to modify TiO₂-based photoanodes for photoelectrochemical (PEC) water splitting. Due to the poor interface contact between chalcogenides and oxides, however, such CdS modified TiO₂ materials usually exhibit inefficient separation and transport of charges, leading to an unsatisfactory efficiency during the PEC water splitting process. Addressing this issue, we herein report a CdS/TiO₂ nanotube array (CdS/TNA) photoanode that was fabricated through a successive ion layer absorption and reaction (SILAR) method with an additional subsequent annealing. This post-annealing process is essential to enhance the interface contact between the CdS and the TNAs, resulting in an accelerated transfer of photogenerated electrons from the CdS to the TNAs. In addition, the post-annealing also improves the light absorption capability of the CdS/TNA photoanode. The simultaneous enhancement of charge transport and light absorption provided by the post-annealing is essential for improving the PEC performance of the CdS/TNA photoanode. The CdS/TNA photoanode obtained by this strategy exhibits a much enhanced PEC performance in water splitting, and its photocurrent density and solar-to-hydrogen conversion efficiency could reach 4.56 mA cm⁻² at 1.23 V vs. reversible hydrogen electrode and 5.61%, respectively. This simple but effective route can provide a general strategy for obtaining high-performance oxide-based photoelectrodes.     

High-efficiency photoelectrochemical water splitting with heterojunction photoanode of In2O3-x nanorods/black Ti–Si–O nanotubes

Constructing heterojunction was an efficient way to promote photoelectrochemical (PEC) water splitting performance of TiO₂-based nano-photoanode. In this work, we demonstrated the feasible preparation of oxygen vacancies-induced In₂O₃ (In₂O_3-x) nanorods/black Si-doped TiO₂ (Ti–Si–O) nanotubes heterojunction photoanode for enhanced PEC water splitting. Black Ti–Si–O nanotubes were fabricated through Zn reduction of the as-annealed Ti–Si–O nanotubes, followed by In₂O_3-x nanorods coupling by a facile electrodepositing and Ar heat treatment. Solar to hydrogen conversion efficiency of the heterojunction photoanode reached as high as 1.96%, which was almost 10 times that of undoped TiO₂. The improved PEC properties were mainly attributed to co-doping effects of Si and Ti³⁺/oxygen vacancy as well as In₂O_3-x decoration, which resulted in enhanced optical absorption and facilitated separation-transport process of photogenerated charge carriers. Charge transfer process in the composite system and hydrogen production mechanism were proposed. This work will facilitate designing TiO₂-based nano-photoanodes for promoting water splitting by integrating with elements doping, oxygen vacancies self-doping and semiconductors coupling.     

Convex-nanorods of α-Fe2O3/CQDs heterojunction photoanode synthesized by a facile hydrothermal method for highly efficient water oxidation

Morphology controlling and surface modification of semiconductors is the key for efficient photoelectrochemical (PEC) water splitting systems. This work provides a new strategy for achieving morphology control and heterojunction construction simultaneously by one-step hydrothermal method. The α-Fe₂O₃/CQDs heterojunction photoanode with convex-nanorods morphology is successfully prepared by hydrothermal method in CQDs (Carbon Quantum Dots) aqueous contained iron precursor followed by low temperature annealing treatment. Compared with bare hematite photoanode, the α-Fe₂O₃/CQDs photoanode has 8.5 time higher photocurrent density (at 1.23 V vs. RHE) of 0.35 mA cm^?2 and a negative shift of onset potential about 300 mV. The enhanced photoelectrochemical response is attributed to the convex-nanorods which benefit higher absorbance of light and the formed α-Fe₂O₃/CQDs heterojunction, which can efficiently enhance the electron-hole separation and reduce the surface charge recombination. The morphology and properties of the sample were characterized with scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fouriertrans form infrared spectroscopy (FTIR), UV–vis spectra, X-ray diffractometry (XRD), X-ray photoelectron spectra (XPS), and photoelectrical measurements.     

Photoelectrochemical study on charge transfer properties of nanostructured Fe2O3 modified by g-C3N4

Novel photocatalysts, which consist of two visible light responsive semiconductors including graphite-like carbon nitride (g-C₃N₄) and Fe₂O₃, were successfully synthesized via electrodeposition followed by chemical vapor deposition. The morphology of the g-C₃N₄/Fe₂O₃ can be tuned from regular nanosheets to porous cross-linked nanostructures. Remarkably, the optimum activity of the g-C₃N₄/Fe₂O₃ is almost 70 times higher than that of individual Fe₂O₃ for photoelectrochemical water splitting. The enhancement of photoelectrochemical activity could be assigned to the morphology change of the photocatalysts and the effective separation and transfer of photogenerated electrons and holes originated from the intimately contacted interfaces. The g-C₃N₄/Fe₂O₃ composites could be developed as high performance photocatalysts for water splitting and other optoelectric devices.     

In2O3:Sn/TiO2/CdS heterojunction nanowire array photoanode in photoelectrochemical cells

The design of photoanode with highly efficient light harvesting and charge collection properties is important in photoelectrochemical (PEC) cell performance for hydrogen production. Here, we report the hierarchical In₂O₃:Sn/TiO₂/CdS heterojunction nanowire array photoanode (ITO/TiO₂/CdS-nanowire array photoanode) as it provides a short travel distance for charge carrier and long light absorption pathway by scattering effect. In addition, optical properties and device performance of the ITO/TiO₂/CdS-nanowire array photoanode were compared with the TiO₂ nanoparticle/CdS photoanode. The photocatalytic properties for water splitting were measured in the presence of sacrificial agent such as SO₃²⁻ and S²⁻ ions. Under illumination (AM 1.5G, 100 mW/cm²), ITO/TiO₂/CdS-nanowire array photoanode exhibits a photocurrent density of 8.36 mA/cm² at 0 V versus Ag/AgCl, which is four times higher than the TiO₂ nanoparticle/CdS photoanode. The maximum applied bias photon-to-current efficiency for the ITO/TiO₂/CdS-nanowire array and the TiO₂ nanoparticle/CdS photoanode were 3.33% and 2.09%, respectively. The improved light harvesting and the charge collection properties due to the increased light absorption pathway and reduced electron travel distance by ITO nanowire lead to enhancement of PEC performance.     

Oxygen evolution NiOOH catalyst assisted V2O5@BiVO4 inverse opal hetero-structure for solar water oxidation

Using vanadium oxide (V₂O₅) inverse opal (IO) as a three-dimensional (3D) electron transporting tunnel, bismuth vanadate (BiVO₄) as a light harvester, and Amorphous Nickel Hydroxide (NiOOH) as an oxygen evolution co-catalyst, a V₂O₅@BiVO₄@NiOOH IO architecture was fabricated as an efficient photoanode on a conductive fluorine doped tin oxide (FTO) substrate for photoelectrochemical (PEC) water oxidation. V₂O₅ is the visible light absorbing photoanodes for water oxidation; however, the efficiency of this compound remains low (∼0.08 mA/cm² at 1.23 V vs. reversible hydrogen electrode (V_RHE)) and the unfavorable surface trap states limits the activity of V₂O₅ photoelectrodes in a PEC system. We found that the photoactive thin conductive BiVO₄ (∼12 nm) in the V₂O₅ IO greatly enhanced the charge separation efficiency to achieve better PEC water oxidation through modification of the surface states. The subsequent addition of NiOOH as an effective Oxygen evolution catalyst subsequently reduces the large overpotential and generates the photocurrent density of 1.14 mA/cm² at 1.23 V_RHE. Electrochemical impedance spectroscopy (EIS) evidenced that NiOOH deposition can substantially lower the charge transfer resistance (R_ct) at the semiconductor interface. Specifically, the consecutive and ordered morphology renders direct conduction pathways for the extraction of photogenerated electron/hole pairs and the convenient structure to penetrate the photogenerated carriers toward the semiconductor surface over the electrolyte. It is expected that the uninterrupted pathways will improve the electron transportation and thus the charge collection properties.     

Enhanced photoelectrocatalytic hydrogen production performance of porous MoS2/PPy/ZnO film under visible light irradiation

Photoelectrochemical (PEC) water splitting provides a “green” approach for hydrogen production. However, the design and fabrication of high-efficient catalysts are the bottleneck for PEC water splitting owing to the involved thermodynamic and kinetic challenges. Herein, we report a new strategy for constructing a porous MoS₂/PPy/ZnO thin film photocatalyst with large specific surface area and excellent conductivity to achieve photoelectrochemical water splitting under visible light irradiation. Porous PPy/ZnO was synthesized via template-assisted electrodeposition, and MoS₂ was further electrodeposited to construct porous MoS₂/PPy/ZnO thin film photocatalyst. The hydrogen evolution rate of MoS₂/PPy/ZnO exhibits about 3.5-fold increase to 40.22 μmol cm⁻² h⁻¹ under visible light irradiation. The enhancement for photoelectrochemical hydrogen production is not only ascribed to enlarged specific surface area of the porous structure, but also attributed to the synergistic effects of MoS₂ and porous PPy/ZnO, which could dramatically improve its visible light absorption capacity and enhance the separation and transfer of photogenerated charges. Thus, more abundant photogenerated electrons and holes participate in photoelectrochemical process, which significantly enhances its photoelectrochemical hydrogen production performance.     

Manipulating the charge separation via piezoelectric field and heterojunction to enhance the photoelectrochemical water splitting ability of Bi2WO6/BiOBr photoanode

The unsatisfactory separation efficiency of photogenerated charge is one of the significant problems restricting the application of photoelectrochemical water splitting. Herein, we successfully prepared a Bi₂WO₆/BiOBr nanoplate arrays structure with the heterostructure for efficient piezoelectric photoelectric water splitting. A charge transfer path is formed by constructing a heterojunction to accelerate the spatial separation of photogenerated charges. The Bi₂WO₆/BiOBr shows the better photoelectrochemical performance with high photocurrent density of 0.068 mA/cm² at 1.23 V vs. RHE which is 1.8 times higher than simple Bi₂WO₆. In addition, after the introduction of piezoelectric polarization, the carrier separation efficiency is further enhanced under the synergistic action of the piezoelectric polarization and the heterojunction, and the photocurrent of Bi₂WO₆/BiOBr photoanode is increased to 0.088 mA/cm² at 1.23 V vs. RHE. By comparing the photoelectrocatalytic performance of the samples before and after the introduction of piezoelectric field, it further explains the role of piezoelectric built-in electric field in promoting carrier separation. This work provides a new method to improve the carrier separation efficiency by combining heterojunction and piezoelectric polarization.     

Enhanced solar-driven water splitting of 1D core-shell Si/TiO2/ZnO nanopillars

In this work, 1D core-shell Si/metal oxide nanopillar (NP) photoanodes were synthesized for enhanced solar-driven water splitting processes. The core-shell structures were fabricated by atomic layer deposition of different metal oxides (TiO₂ and ZnO) onto Si NP, which were synthesized by metal-assisted chemical etching and nanosphere lithography. In order to characterize produced photoanodes various experimental techniques (SEM/TEM, XRD, Transmittance, Reflectance, Raman spectroscopy) were applied. Photoelectrochemical (PEC) water oxidation of produced photoanodes was studied. It was shown that composition of n-Si/TiO₂/ZnO NP exhibited enhanced photocurrents due to barrier effects. The enhanced PEC properties of core-shell Si/TiO₂/ZnO NP are caused by efficient charge separation of photogenerated electron-hole pairs in the TiO₂/ZnO shell and effective holes transfer to the shell-electrolyte interface. The superior photoelectrochemical performance of a photoanode based on core-shell Si/TiO₂/ZnO NP has been confirmed through electrochemical impedance spectroscopy and voltamperometric measurements under electrode irradiation. 1D core-shell Si/TiO₂/ZnO NP offer a new approach for preparing stable and highly efficient photoanodes for PEC water-splitting process.     

Investigation of the annealing treatment on the performance of TiO2 photoanode

Developing low-cost semiconductor photoanode toward efficient and stable oxygen evolution reaction (OER) is highly desirable for photoelectrochemical (PEC) water splitting. Herein, nanoparticulate titanium dioxide (TiO₂) electrodes were prepared using Degussa P25 powders by spin-coating method. The effects of annealing conditions on the PEC performance of the nanoparticulate TiO₂ photoanode was systematically investigated including temperature, annealing time and atmosphere. The results demonstrate that the TiO₂/fluorine-doped tin oxide substrates (FTO/TiO₂) electrode annealed at argon (Ar) atmosphere under 450 °C shows the highest PEC performance. The photocurrent density of FTO/TiO₂ annealed in Ar for only 0.5 h reached to 120 μA/cm² at 0.3 V vs. Hg/HgO which is about 10 times higher than that of the unannealed one. The X-ray photoelectron spectroscopy (XPS) results show the thermal treatment can produce oxygen vacancies on the surface of TiO₂ which reduce the recombination of photogenerated electron-hole pairs and expanding the visible light absorption by introducing defective energy levels. The electrochemical impedance spectroscopy (EIS) approves that appropriate annealing treatment can effectively enhance the electron conductivity resulting in low charge transfer resistance. All these factors contribute to improving the PEC activity of TiO₂ photoanode.     

Nanostructured SrTiO3 thin films sensitized by Cu2O for photoelectrochemical hydrogen generation

We prepared nanostructured thin films of pristine SrTiO₃, Cu₂O and SrTiO₃/Cu₂O heterojunction with varying the thickness of Cu₂O. SrTiO₃ and Cu₂O thin films were deposited on ITO (Sn:In₂O₃) glass substrate using sol–gel spin-coating technique and spray pyrolysis method respectively. Samples were characterized using XRD (X-ray diffractometry), SEM (Scanning electron microscopy), and UV–Visible absorption spectroscopy. Nanostructured thin films of pristine SrTiO₃, Cu₂O and SrTiO₃/Cu₂O heterojunction systems were used as photoelectrode in the Photoelectrochemical (PEC) cell for water splitting reaction. Maximum photocurrent density value of 2.44 mA cm⁻² at 0.95 V/SCE were observed for SrTiO₃/Cu₂O heterojunction photoelectrode with 454 nm thickness, which was approximately 34 times higher than pristine SrTiO₃ thin film. Increased photocurrent density observed for the heterojunction can be attributed to the improved conductivity and better separation of the photogenerated charge carriers at the SrTiO₃/Cu₂O interface.     

Enhanced photoelectrochemical performance of TiO2 through controlled Ar+ ion irradiation: A combined experimental and theoretical study

Here we demonstrate that the performance of TiO₂ electrodes for photoelectrochemical water oxidation can be effectively enhanced through oxygen vacancy doping. The ion irradiation is a simple method to introduce oxygen vacancies on the surface and into the interior of TiO₂ for making oxygen-deficient titania (TiO_2-x). The TiO_2-x thin films exhibit obvious increase in the performance of photoelectrochemical water splitting under light irradiation. The photoconversion efficiency η of the TiO_2-x photoanode is 0.5-fold higher than that of the pristine TiO₂ photoanode, which benefits from the introducing of oxygen vacancies produced by ion irradiation. While the irradiation-induced titanium vacancies act as trapping centers for charge carriers and decrease the photoelectrochemical performance of the samples. Positron annihilation spectroscopy (PAS) was used to study the type of the formed vacancies. Combining experimental with theoretical study, this study demonstrates that ion irradiation technique combing with thermal annealing could be an effective way to enhance the performance of photoanode for water splitting.     

An efficient tandem photoelectrochemical cell composed of FeOOH/TiO2/BiVO4 and Cu2O for self-driven solar water splitting

An integrated solar water splitting tandem cell without external bias was designed using a FeOOH modified TiO₂/BiVO₄ photoanode as a photoanode and p-Cu₂O as a photocathode in this study. An apparent photocurrent (0.37 mA/cm² at operating voltage of +0.36 V_RHE) for the tandem cell without applied bias was measured, which is corresponding to a photoconversion efficiency of 0.46%. Besides, the photocurrent of FeOOH modified TiO₂/BiVO₄–Cu₂O is much higher than the operating point given by pure BiVO₄ and Cu₂O photocathode (∼0.07 mA/cm² at +0.42 V_RHE). Then we established a FeOOH modified TiO₂/BiVO₄–Cu₂O two-electrode system and measured the current density-voltage curves under AM 1.5G illumination. The unassisted photocurrent density is 0.12 mA/cm⁻² and the corresponding amounts of hydrogen and oxygen evolved by the tandem PEC cell without bias are 2.36 μmol/cm² and 1.09 μmol/cm² after testing for 2.5 h. The photoelectrochemical (PEC) properties of the FeOOH modified TiO₂/BiVO₄ photoanode were further studied to demonstrate the electrons transport process of solar water splitting. This aspect provides a fundamental challenge to establish an unbiased and stabilized photoelectrochemical (PEC) solar water splitting tandem cell with higher solar-to-hydrogen efficiency.     

Enhanced efficiency of hematite photoanode for water splitting with the doping of Ge

Ge doped α-Fe₂O₃ nanowires are synthesized through a hydrothermal procedure with GeO₂ as a precursor and investigated as photoanodes for water splitting. The content of Ge in the photoanode rises with the increase of the amount of GeO₂ in the precursor solution. A proper amount of Ge facilities the preferred oriented growth of the (110) plane of α-Fe₂O₃, while excessive Ge hinders the growth of α-Fe₂O₃ crystals. The doping of Ge increases the absorption efficiency and decreases the recombining rate of the photogenerated electrons and holes. Ge also improves the density and transfer rate of the charge carriers in the photoanode. Ge doped α-Fe₂O₃ photoanode exhibits a highest photocurrent density of 0.92 mA cm^?2 at 1.23 V vs. reversible hydrogen electrode under AM 1.5 G simulated sunlight, which is nearly twice of that obtained by pure α-Fe₂O₃ under the same condition.     

The co-decorated TiO2 nanorod array photoanodes by CdS/CdSe to promote photoelectrochemical water splitting

A cascade structure of TiO₂/CdS/CdSe semiconductor heterojunction is synthesized using a three-step technique of facile hydrothermal growth for the enhancement of the photoelectrochemical performances. The optical and photoelectrochemical properties controlled by the deposition processing parameters have been investigated. It is shown that the patterns of semiconductor heterojunction enlarge the absorption range of solar spectra, and improve the properties of the photogenerated charge carriers describing separation and transportation, and reduce the interface resistance between the photoelectrode and electrolyte comparing with the pure TiO₂ and CdS-decorated TiO₂ nanorod array photoanodes. The higher photocurrent density and photoconversion efficiency are up to 4.23 mA cm⁻² and 4.2%, which are the 4.1 and 25.3 times superior than that of the pure TiO₂ photoanode. The hydrothermal growth time increment of CdSe yields greater photoelectrochemical water splitting performances. The underlying physics mechanisms have been discussed based on forming a type-Ⅱ energy band alignment structure.     

Ultrathin hematite films deposited layer-by-layer on a TiO2 underlayer for efficient water splitting under visible light

Ultrathin hematite (α-Fe₂O₃) film deposited on a TiO₂ underlayer as a photoanode for photoelectrochemical water splitting was described. The TiO₂ underlayer was coated on conductive fluorine-doped tin oxide (FTO) glass by spin coating. The hematite films were formed layer-by-layer by repeating the separated two-phase hydrolysis-solvothermal reaction of iron(III) acetylacetonate and aqueous ammonia. A photocurrent density of 0.683 mA cm⁻² at +1.5 V vs. RHE (reversible hydrogen electrode) was obtained under visible light (>420 nm, 100 mW cm⁻²) illumination. The TiO₂ underlayer plays an important role in the formation of hematite film, acting as an intermediary to alleviate the dead layer effect and as a support of large surface areas to coat greater amounts of Fe₂O₃. The as-prepared photoanodes are notably stable and highly efficient for photoelectrochemical water splitting under visible light. This study provides a facile synthesis process for the controlled production of highly active ultrathin hematite film and a simple route for photocurrent enhancement using several photoanodes in tandem.